JPH1067922A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition excellent in impact resistance and flame resistance etc., without using a chloride and a bromide compounds by formulating a fluorine-based resin and a specific phosphoric acid ester with a mixture of a copolyester, an aromatic polycarbonate and an ABS resin. SOLUTION: This theremolastic resin composition comprises the formulation of (A) (i) a polymer mixture of a copolyester having 95/5 to 10/90 mol ratio of an ethylene glycol unit to a cyclohexanedimethanol unit and an aromatic polycarbonate, (ii) a grafted copolymer composed of a monomer mixture containing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer and another vinyl-based monomer copolymerizable with these monomer, and a gum polymer, and/or (iii) a vinyl-based copolymer composed of the before monomer mixture, (B) 0.01-5 pts.wt. fluorine-based resin and/or 0.01-5 pts.wt. silicone and (C) 1-40 pts.wt. compound containing phosphorus based on 100 pts.wt. resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing no chlorine and bromine compounds, which is excellent in flame retardancy and excellent in impact resistance, heat resistance and moldability.

[0002]

2. Description of the Related Art Plastics have excellent mechanical properties,
Due to its moldability and electrical insulation, it is used in a wide range of fields including home electric appliances, OA appliances, automobiles and other parts. However, most plastics are flammable, and various techniques have been devised to resist flame retardation due to safety issues.

[0003] Generally, a method is employed in which a halogen-based flame retardant such as a bromine compound having a high flame-retardant efficiency and antimony oxide are blended with a resin to make the resin flame-retardant. However,
This method has problems such as a large amount of smoke generated during combustion.

[0004] In recent years, in order to overcome the drawbacks of these halogen-based flame retardants, a flame-retardant resin containing no halogen has been strongly desired.

A thermoplastic resin composition comprising a PBT alloy and a resorcinol type aromatic phosphate oligomer (EP 491986), comprising a polyalkylene terephthalate, a resorcinol type aromatic bisphosphate, melamine cyanurate and a filler. A thermoplastic resin composition (JP-A-5-70671), a thermoplastic resin composition comprising polybutylene terephthalate and polycarbonate, and a resorcin-type aromatic bisphosphate (JP-A-6-504563) have been proposed. ing.

[0006]

The flame-retardant thermoplastic resin composition for use in injection-molded articles, especially household electric equipment, electronic equipment, OA equipment parts and their housings, and automobile parts, has excellent flame retardancy. It is required to have both mechanical properties represented by impact resistance and moldability.

However, EP-A-49198.
No. 6, JP-A-5-70671, JP-T-Hei-6-5
The composition described in JP 04563 was inferior in impact resistance and was not satisfactory.

An object of the present invention is to provide a resin composition which is excellent in impact resistance, fluidity during molding, and flame retardancy without using chlorine and bromine compounds while utilizing the inherent properties of the resin. I do.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present invention has found that a mixture of a copolyester having a specific amount of cyclohexanedimethanol unit, an aromatic polycarbonate and an ABS resin contains a fluorine resin and an ABS resin. The present inventors have found that the above object can be efficiently achieved by blending a specific phosphate ester, and have reached the present invention.

That is, the present invention relates to "(A) (a) comprising a condensation unit of ethylene glycol, 1,4-cyclohexanedimethanol and terephthalic acid, wherein the molar ratio of ethylene glycol unit to cyclohexanedimethanol unit is 95/5 to 5/5. A polymer mixture consisting of 95 to 5% by weight of a 10/90 copolyester and (b) 5 to 95% by weight of an aromatic polycarbonate; and (B) 20 to 90% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer. A rubbery polymer 1 to 99 to 20 parts by weight of a monomer mixture containing 1 to 60% by weight of a monomer and 0 to 79% by weight of another vinyl monomer copolymerizable therewith is used.
A graft copolymer obtained by graft copolymerization to 80 parts by weight, and / or (C) 20 to 90% by weight of an aromatic vinyl monomer and 1 to 60% by weight of a vinyl cyanide monomer, and A resin composition (a) comprising a vinyl copolymer obtained by copolymerizing a monomer mixture containing 0 to 79% by weight of another copolymerizable vinyl monomer (component (A): 10-98
(D) 0.01 to 5 parts by weight of a fluorinated resin and / or 0.01 to 5 parts by weight of silicone per 100 parts by weight of 100% by weight (the sum of the components (B) and (C) is 90 to 2% by weight). Parts by weight and (E) 1 to 40 parts by weight of a phosphorus-containing compound. "

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In the present invention, “weight” means “mass”.

The copolyester (a) constituting the component (A) used in the present invention can be obtained from commercial products. For example, poly (ethylenecyclohexane dimethylene terephthalate)
A copolyester material known as "Easter GN002" and "Easter DN003" is commercially available from Eastman Kodak Company. The copolyester (A) used in the present invention preferably has a logarithmic viscosity of 0.4 to 2.0 dl / g when measured in a 60/40 (weight ratio) mixed solvent of phenol and tetrachloroethane at 25 ° C. More preferably, 0.6 to
1.2 dl / g.

The copolyester (a) used in the present invention may contain isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid in an amount of not more than 20 mol%, preferably not more than 10 mol% of the acid component or diol component. Acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4′-
Biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 1,2-bis (4-carboxyphenoxy)-
Other dicarboxylic acids such as ethane, succinic acid, adipic acid, speric acid, azelaic acid, sebacic acid, dodecadionic acid, octadecanedicarboxylic acid, dimer acid and 1,4-cyclohexanedicarboxylic acid or propylene glycol, 1,6-hexanediol Others, such as 1,8-octanediol, 1,10-decanediol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and 2,2-bis (2'-hydroxyethoxyphenyl) propane Those substituted with a diol can also be used.

The copolyester (a) has a molar ratio of constituent ethylene glycol units to cyclohexane dimethanol units of 10/90 to 95/5, preferably 20/90.
80 to 80/20. When the molar ratio of the copolyester is out of the above range, it is not preferable because excellent mechanical properties such as flame retardancy and impact resistance are balanced to obtain an excellent composition.

The component (A) according to the present invention comprises
b) As aromatic polycarbonates, generally, 2,2
-Bis (4-oxyphenyl) alkane, bis (4-
It is a polymer or copolymer composed of bisphenols such as (oxyphenyl) ether type, bis (4-oxyphenyl) sulfone, sulfide or sulfoxide type. Aromatic polycarbonate is produced by any method. For example, in the production of polycarbonate from 4,4'-dihydroxydiphenyl-2,2-propane (commonly known as bisphenol A), the phosgene method is carried out by blowing phosgene in the presence of a caustic aqueous solution and a solvent. Or 4,4'-dihydroxydiphenyl-2,2
A method in which propane and a carbonic acid diester are transesterified in the presence of a catalyst to produce the same;

Although the molecular weight of the aromatic polycarbonate is not particularly limited, the intrinsic viscosity measured at 30 ° C. in a tetrahydrofuran solvent is 0.30 to 0.60 dl / g, particularly 0.35 dl / g.
A thermoplastic resin composition having a range of from about 0.50 dl / g to about 0.50 dl / g is preferably excellent in balance between impact resistance and fluidity during melt molding.

The component (A) of the present invention comprises (a) 95 to 5% by weight, preferably 70 to 10% by weight of a copolyester, and (b) 5 to 95% by weight, preferably 30 to 90% by weight of an aromatic polycarbonate. Consists of a range. (A) When the proportion of the copolyester exceeds 95% by weight, the heat resistance, impact resistance and flame retardancy of the obtained resin composition deteriorate, and when it is less than 5% by weight, the moldability tends to deteriorate.

The graft copolymer (B) in the present invention refers to a rubbery polymer in an amount of 1 to 80 parts by weight, a monomer mixture of an aromatic vinyl monomer and a vinyl cyanide monomer of 99 to 2 parts.
It is a graft copolymer obtained by graft-polymerizing 0 parts by weight. The term “(B) graft copolymer” used herein includes not only a material having a structure obtained by graft copolymerization with a rubbery polymer but also a non-grafted copolymer.

As the rubbery polymer, those having a glass transition temperature of 0 ° C. or less are suitable, and diene rubbers are preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer,
Examples include diene rubbers such as butyl acrylate-butadiene copolymer, acrylic rubbers such as polybutyl acrylate, polyisoprene, and ethylene-propylene-diene terpolymer. Among them, polybutadiene or butadiene copolymer is preferred.

The rubber particle diameter of the rubbery polymer is not particularly limited, but the weight average particle diameter of the rubber particles is 0.15 to 0.6.
Those having a thickness of 0 μm, especially 0.18 to 0.40 μm are preferable because of excellent impact resistance, flame retardancy and color tone.

As the aromatic vinyl monomer, styrene,
Examples include α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, etc., with styrene being particularly preferred.

Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferred.

If necessary, a graft copolymerizable vinyl monomer, for example, a maleimide monomer such as maleimide, N-methylmaleimide or N-phenylmaleimide, methyl or ethyl (meth) acrylate, Propyl,
α, β-unsaturated carboxylic acid alkyl esters such as n-butyl and the like can be used. Further, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid and anhydrides thereof, acrylamide, 2-hydroxyethyl (meth) acrylate, (meth) By using a vinyl monomer having a functional group such as glycidyl acrylate,
The compatibility with the component (A) is further improved, and the mechanical properties of the obtained resin composition can be improved.

The monomer mixture used in the graft copolymer (B) contains at least 20% by weight, preferably at least 22% by weight, and at most 90% by weight of an aromatic vinyl monomer.
The content is preferably 80% by weight or less, and the content of the vinyl cyanide monomer is 1% by weight or more, preferably 2% by weight or more, and 60% by weight or less, preferably 50% by weight or less. Used. In addition to the aromatic vinyl monomer and the vinyl cyanide monomer, other vinyl monomers copolymerizable therewith can be added, and the amount is 79% by weight or less, further 76% by weight. % Is preferably used. When the ratio of the aromatic vinyl monomer is 20
When the content is out of the range of 90% by weight, the impact resistance of the resin composition tends to be poor. When the proportion of the vinyl cyanide monomer exceeds 60% by weight, the thermal stability of the graft copolymer is remarkably reduced, and the resin composition tends to have a poor color tone.

(B) The ratio of the rubbery polymer to the monomer mixture when the graft copolymer is obtained is 1 part by weight or more, preferably 5 parts by weight, of the rubbery polymer based on 100 parts by weight of the total graft copolymer. Not less than 80 parts by weight, preferably not more than 70 parts by weight,
Parts by weight or less are used. The amount of the monomer mixture is at most 99 parts by weight, preferably at most 95 parts by weight, at least 20 parts by weight, preferably at least 30 parts by weight. Although the object of the present invention can be achieved even when the proportion of the rubbery polymer is 0, the content is preferably 1 part by weight or more, in order to further improve the impact resistance of the resin composition, or a good molded product appearance of the resin composition. To obtain it, the amount is preferably 80 parts by weight or less.

(B) The graft copolymer can be obtained by a known polymerization method. For example, it can be obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier are continuously supplied to a polymerization vessel in the presence of a rubbery polymer latex to carry out emulsion polymerization.

(B) The graft copolymer contains a non-grafted copolymer in addition to a material having a structure grafted to a rubbery polymer. (B) The graft ratio of the graft copolymer is not particularly limited. However, in order to obtain a resin composition having an excellent balance of impact resistance, flame retardancy and gloss, the graft ratio is preferably 20 to 20%.
120% by weight, especially 30-70% by weight, is preferred. Here, the graft ratio is calculated by the following equation. Graft ratio (%) = <amount of vinyl copolymer graft-polymerized on rubbery polymer> / <rubber content of graft copolymer> × 100

The properties of the non-grafted copolymer are not particularly limited, but (B) intrinsic viscosity [η] of the methyl ethyl ketone soluble portion of the graft copolymer (measured at 30 ° C.)
Is from 0.25 to 0.6 dl / g, especially from 0.30 to 0.5
The range of 5 dl / g is preferably used because a resin composition having excellent impact resistance is obtained.

In the resin composition of the present invention, if necessary, a vinyl copolymer (c) having a polymerized structure derived from an aromatic vinyl monomer and a vinyl cyanide monomer is blended. . Styrene, α as the aromatic vinyl monomer
-Methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, o-ethylstyrene, and the like, with styrene being particularly preferred. One or more of these can be used.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, and ethacrylonitrile, and acrylonitrile is particularly preferable.

If necessary, other vinyl monomers,
For example, maleimide monomers such as maleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide, and ester compounds of (meth) acrylic acid such as methyl, ethyl, propyl, and n-butyl are used. Further, vinyl monomers containing a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl Glycidyl ether, styrene-p-glycidyl ether, vinyl monomers containing an epoxy group such as p-glycidylstyrene, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, Phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, acrylamide, Takuriruamido, N-
Methyl acrylamide, butoxymethyl acrylamide, N-propyl methacrylamide, vinyl monomers having an amino group or a substituted amino group such as styrene having an amino group bonded to a benzene ring, 2-hydroxyethyl acrylate, 2-hydroxy methacrylate Ethyl, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6 methacrylate
Pentahydroxyhexyl, acrylic acid 2,3,4
5-tetrahydroxypentyl, methacrylic acid 2,3
4,5-tetrahydroxypentyl, 3-hydroxy-
1-propene, 4-hydroxy-1-butene, cis-4
-Hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, 1 Compatibility of component (A) with component (B) and component (C) is improved by incorporating a polymer structure derived from a vinyl monomer having a hydroxyl group such as 1,4-dihydroxy-2-butene. However, the mechanical properties of the resin composition can be further improved.

Here, the ratio of each component derived from the monomer mixture of the aromatic vinyl monomer is 20% by weight or more, preferably 40% by weight or more, and 90% by weight or less.
It is preferably at most 80% by weight, and the amount of the vinyl cyanide monomer is at least 1% by weight, preferably at least 2% by weight,
Also, it is at most 60% by weight, preferably at most 50% by weight.
79% by weight or less, preferably 58% by weight of another vinyl monomer
% By weight or less.

In the vinyl copolymer (C), if the content of the aromatic vinyl monomer is out of the range of 20 to 90% by weight, the impact resistance of the resin composition deteriorates, which is not preferable. The molecular weight of the vinyl copolymer (C) is not particularly limited, but the intrinsic viscosity [η] (N, N-dimethylformamide solvent, measured at 30 ° C) is 0.35 to 0.8.
Those having 5 dl / g, particularly 0.4 to 0.6 dl / g, are preferably used because a resin composition having excellent impact resistance and moldability can be obtained.

(C) The method for producing the vinyl copolymer is not particularly limited, and may be any of ordinary methods such as bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, and solution-bulk polymerization. Can be used.

The resin composition (A) defined in the present invention comprises:
It consists of the polymer mixture (A), graft copolymer (B) and vinyl copolymer (C) described above. The polymer mixture (A) is 10% by weight or more, preferably 40% by weight or more, and 98% by weight or less, preferably 9% by weight or less.
It is blended in a range of 5% by weight or less. Further, at least one of the graft copolymer (B) and the vinyl copolymer (C)
The copolymers are blended, and the total of the components (B) and (C) is 2% by weight or more, preferably 5% by weight or more, and 90% by weight or less, preferably 60% by weight in the resin composition (A). It is blended at a ratio of not more than% by weight.

There are two more preferable blending amounts. One is that the amount of component (C) in the resin composition (a) is 2 to 90 in addition to the above blending amount.
% By weight. As another preferable compounding amount, in the resin composition (a), the component (B) is 2 to 9
0% by weight and the component (C) is 0 to 88% by weight.

In the latter case, the graft copolymer (B)
Is 90% by weight or less, preferably 60% by weight or less, and 2% by weight.
% By weight, preferably 5% by weight or more. The vinyl copolymer (C) is blended in an amount of 88% by weight or less, preferably 55% by weight or less, 0% by weight or more, preferably 1% by weight or more, and more preferably 5% by weight or more. Is done.

The polymer mixture (A) is a resin composition (a)
If it is less than 10% by weight, the flame retardancy and impact resistance will be poor, and if it exceeds 98% by weight, the impact resistance will be poor, which is not preferable.

The composition of the present invention contains (D) a fluorine resin or silicone. Here, these combinations are also possible. The fluorine-based resin is a polymer having a tetrafluoroethylene structure, and preferably has a fluorine content of 65 to 76% by weight, and more preferably 70 to 76% by weight.
It has. Examples thereof include a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer of tetrafluoroethylene and an ethylenically unsaturated monomer containing no fluorine.

The method for producing the fluororesin is not particularly limited. For example, in a water-based medium, using a catalyst such as sodium, potassium or ammonium peroxydisulfate, 7-71.
At a temperature of 0 to 200 ° C. under a pressure of kg / cm 2,
A known method such as polymerization of tetrafluoroethylene or the like can be used.

The fluororesin usually has a specific gravity of 2.0 to 2.5.
g / cm 3 and a powder having a melting point of 310 to 350 ° C. are used, but are not particularly limited. The shape of the fluororesin is arbitrary, but preferably, a powdery one having a particle diameter (secondary) of 10 to 600 μm measured by ASTM D1457 is used.

The amount of the fluororesin (D) used in the present invention is preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin composition (a), from the viewpoint of flame retardancy and mechanical properties of the molded article. Is 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight.
Parts by weight. (D) The amount of the fluorine-based resin is 0.01
If the amount is less than 5 parts by weight, the flame retardancy of the thermoplastic resin composition deteriorates. If the amount exceeds 5 parts by weight, the impact resistance of the thermoplastic resin composition deteriorates, which is not preferable.

The silicone which is another component (D) is an organopolysiloxane, which is a polymer of dimethylsiloxane, a polymer of phenylmethylsiloxane, a polymer of diphenylsiloxane, a polymer of methylethylsiloxane, methylpropyl Examples thereof include siloxane polymers and copolymers thereof. Further, a modified silicone in which the terminal or side chain of the molecular structure is substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an organic group having an ether bond, or the like is also useful. The number average molecular weight of the silicone is not particularly limited, but the lower limit is preferably 200, more preferably 1,000, and the upper limit is 5,000,000.
A range of 0 is preferred. Any shape such as oil, gum, varnish, powder, and pellet can be used as the silicone.

The amount of silicone added is from 0.01 to 5 parts by weight, preferably from 0.05 to 2 parts by weight, per 100 parts by weight of the resin composition (a) from the viewpoint of flame retardancy and mechanical properties of the molded article. , More preferably 0.1 to 1 part by weight. (D) If the blending amount of the fluororesin is less than 0.01 part by weight, the flame retardancy of the thermoplastic resin composition is deteriorated, and if it exceeds 5 parts by weight, the impact resistance of the thermoplastic resin composition is deteriorated, which is preferable. Absent.

The (E) phosphorus-containing compound used in the present invention includes inorganic polyamines such as ammonium polyphosphate, ammonium pyrophosphate, phosphazene compounds and red phosphorus modified with triazine compounds such as ammonium polyphosphate, melamine and benzoguanamine. Examples include a phosphorus compound and an organic phosphorus compound of the following formula (I).

[0046]

Embedded image (However, the above formulas R ^{1 to} R ⁹ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Ar
^{1, Ar 2, Ar 3,} Ar 4, Ar 5, Ar 6, Ar 7
Represents the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ ,
Represents CH ₂ or CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. K and m are each 0
Is an integer of 2 or more and k + m is an integer of 0 or more and 2 or less. )

First, the structure of the flame retardant represented by the formula (I) will be described. In the formula (I), k and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less.
An integer of 1 or more and 1 or less, particularly preferably k and m are each 1
It is.

When n is converted into a number average polymerization, n is preferably 0.5 or more. This value is G
It can be measured by PC (Gel Permeation Chromatography).

In the formula (I), R ^{1 to} R ⁹ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-
Examples thereof include a butyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, and a neopentyl group. Among them, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted by halogen-free organic residues. Specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group.A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferred. Particularly, a phenyl group, a tolyl group and a xylyl group are preferred.

Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group.

The phosphorus-containing compound represented by the formula (I) can be produced according to the following chemical reaction formula (II).

[0053]

Embedded image (In the above formula, the description of each functional group is the same as in the case of (I).)

As the phosphorus-containing compound (E) used in the present invention, a salt composed of cyanuric acid or isocyanuric acid and a triazine compound such as melamine can be used in combination, if necessary.

In the present invention, the compounding amount of the (E) phosphorus-containing compound is 1 to 40 with respect to 100 parts by weight of the resin composition (a).
Parts by weight, preferably 4 to 30 parts by weight. If the amount of the (E) phosphorus-containing compound is less than 1 part by weight, the flame retardancy will be poor, and if it exceeds 40 parts by weight, the impact resistance of the thermoplastic resin composition will be poor, which is not preferable.

The composition of the present invention may further contain (F) a phenolic resin. Such resins are
Any polymer may be used as long as it has a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type and heat-reactive resins, and resins modified from these.
(F) The phenolic resin is not particularly limited, and a commercially available resin is used. For example, in the case of a novolak type phenol resin, phenols and aldehydes are charged into a reaction tank at a molar ratio of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluene sulfone are further added. After adding a catalyst such as an acid, the mixture is heated and refluxed for a predetermined time. Vacuum dehydration or static dehydration to remove generated water, and further, a method of removing remaining water and unreacted phenols can be obtained. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components can be used alone or in combination of two or more.

In the case of a resole type phenol resin,
The molar ratio of phenols to aldehydes is 1: 1 to 1: 2
After charging into a reaction tank in such a ratio as follows, adding a catalyst such as sodium hydroxide, aqueous ammonia, and other basic substances, the same reaction and treatment as for the novolak-type phenol resin can be performed.

Here, phenols are phenol, o
-Cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-
Methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert
-Butyl-p-cresol and the like. One or more of these phenols can be used.
On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. One or more of these aldehydes can be used as needed.

The molecular weight of the phenolic resin is not particularly limited, but is preferably in the range of 300 to 2,000 in number average, and particularly in the range of 500 to 1,500 is excellent in mechanical properties, moldability and economical efficiency. preferable. The phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a phenol resin standard sample.

The addition amount of the phenolic resin (F) in the present invention is from 0 to 100 parts by weight from 100 parts by weight of the resin composition (a) from the viewpoint of flame retardancy and mechanical properties of the molded article, and especially impact resistance.
20 parts by weight, preferably 0 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

The method for producing the resin composition of the present invention is not particularly limited. For example, (1) a polymer blend obtained by melt-kneading (A) (a) a copolyester and (b) an aromatic polycarbonate; Graft copolymer,
A mixture of (C) a vinyl copolymer, (D) a fluorine resin and (E) a phosphorus-containing compound,
Melt and knead with rolls, extruders, kneaders, etc.
(2) A mixture of (a) a copolyester, (b) an aromatic polycarbonate, (B) a graft copolymer, (C) a vinyl copolymer, (D) a fluororesin, and (E) a phosphorus-containing compound. It is commercialized by melt-kneading with a mixer, roll, extruder, kneader, etc.

[0062] The thermoplastic resin composition of the present invention may contain other thermoplastic resins. For example, impact resistance and heat resistance can be improved by mixing polyphenylene ether, polyglutarimide and the like, and flame retardancy and chemical resistance can be improved by mixing epoxy group-containing polyolefin and polyamide. Further, if necessary, fillers such as glass fiber, talc, and potassium whisker titanate, various stabilizers such as hindered phenolic antioxidants and ultraviolet absorbers, pigments, dyes, lubricants and plasticizers can also be added. it can.

The thermoplastic resin composition of the present invention can be melt molded and used as a resin molded product.

This resin molded product is useful for housings of OA equipment, home electric appliances, etc. and their parts because of their flame retardancy and other features. In particular, even in the case molded product having a minimum thickness of 2 mm or less, sufficient flame retardancy can be obtained, so that it can be widely used for various OA devices and home appliances.

[0065]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In addition, the number of parts and% in an Example show a weight part and weight%, respectively.

Reference Example 1 (A) Preparation of Polymer Mixture <A-1>"Easter" GN in which terephthalic acid is used as a dicarboxylic acid component and the molar ratio of ethylene glycol units to cyclohexanedimethanol units is estimated to be 70/30.
002 (manufactured by Eastman Kodak) and a tetrahydrofuran solvent having an intrinsic viscosity of 0.48 measured at 30 ° C.
<A-1> was prepared by melt-kneading a mixture of 80% of dl / g of an aromatic polycarbonate with a twin-screw extruder.

<A-2>"Easter" DN002 (manufactured by Eastman Kodak Co., Ltd.), in which terephthalic acid is used as a dicarboxylic acid component and the molar ratio of ethylene glycol units to cyclohexane dimethanol units is estimated to be 30/70.
Aromatic polycarbonate 4 having an intrinsic viscosity of 0.48 dl / g measured at 30 ° C. in 0% and a tetrahydrofuran solvent.
<A-2> was prepared by melt-kneading the 0% mixture with a twin-screw extruder.

<A-3>"Easter" GN002 (manufactured by Eastman Kodak Co.), whose molar ratio of ethylene glycol units to cyclohexanedimethanol units is estimated to be 70/30, was used.

<A-4> In a tetrahydrofuran solvent, 3
An aromatic polycarbonate having an intrinsic viscosity of 0.48 dl / g measured at 0 ° C. was used.

<A-5> PBT1200 (manufactured by Toray Industries, Inc.), which is polybutylene terephthalate, was used.

Reference Example 2 (B) Preparation of Graft Copolymer The method for preparing the graft copolymer is described below. The graft ratio was determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. This solution was centrifuged at 8000 rpm (10,000 G) for 30 minutes, and then the insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured. Graft ratio = [(n) − (m) × L] / [(m) × L]
× 100 Here, L means the rubber content of the graft copolymer.

<B-1> 60 parts of polybutadiene latex (average rubber particle diameter 0.32 μm, gel content 88%)
40 parts of a monomer mixture composed of 70% of styrene and 30% of acrylonitrile was emulsion-polymerized in the presence of (solid content). The obtained graft copolymer was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered and dried to prepare a powdery graft copolymer (B-1).

The obtained graft copolymer was measured by the same method as in B-1, and the graft ratio was 38%. This graft copolymer contained 17% of a non-graft copolymer composed of 70% of styrene structural units and 30% of acrylonitrile structural units. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.37 dl / g. <B-2> 45 parts of polybutadiene latex (average rubber particle diameter 0.21 μ, gel content 80%) (in terms of solid content)
55 parts of a monomer mixture consisting of 79% of styrene and 21% of acrylonitrile was emulsion-polymerized in the presence of the above. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (B-2).

The obtained graft copolymer had a graft ratio of 41%. Further, this graft copolymer has a styrene structural unit of 79% and an acrylonitrile structural unit of 2%.
It contained 36% of a 1% non-graftable copolymer. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.43 dl / g. Reference Example 3 (C) Preparation of vinyl copolymer <C-1> A monomer mixture of 72% styrene and 28% acrylonitrile was subjected to suspension polymerization to prepare a copolymer (C-1). The intrinsic viscosity of the N, N-dimethylformamide-soluble component of the obtained copolymer was 0.61 dl / g. <C-2> Styrene 50%, N-phenylmaleimide 3
A monomer mixture of 0% and acrylonitrile 20% was emulsion-polymerized to prepare a copolymer (C-2).

The copolymer obtained had an intrinsic viscosity of 0.56 dl / g of N, N-dimethylformamide-soluble component.

Reference Example 4 (D) Fluorine-based resin or silicone <D-1> Polyflon F201 which is polytetrafluoroethylene (manufactured by Daikin Industries, Ltd.) (ASTM D)
Particle size (secondary) measured at 1457 is 0.5 mm, melting point 3
40 ° C.).

<D-2>"Trefoil" E-601 (Dow Corning Toray, an epoxy group-modified silicone)
Silicone Co., Ltd.) was used.

Reference Example 5 (E) Phosphorus-Containing Compound The compounds having the following chemical structural formulas (A), (B), (C) and (D) were used.

[0079]

Embedded image

Reference Example 6 (F) Phenol resin Novolak type phenol resin having a number average molecular weight of 700 (P
R-53195, manufactured by Sumitomo Durez Co., Ltd.).

Examples 1 to 17 (A) Polymer mixture, (B) graft copolymer, (C) vinyl copolymer, (D) fluorine resin, (E) phosphorus-containing compound, And (F) a phenolic resin in the mixing ratio shown in Table 1 and a vented 30 mmφ2
A pellet-shaped polymer was manufactured by melt-kneading and extruding at a resin temperature of 220 ° C. with a screw extruder. Next, a test piece was molded by an injection molding machine at a cylinder temperature of 220 ° C. and a mold temperature of 60 ° C., and the physical properties were measured under the following conditions.

1/4 "Izod impact strength: ASTM
D256-56A 1/8 "Izod impact strength: ASTM D256-5
6A Heat distortion temperature: ASTM D648 (test thickness: 1/4 ")
18.56 kg / cm ² load) MFR (Melt flow rate value): JIS K7210
(220 ° C., 2160 g) A larger value means better fluidity during molding. Flame resistance: According to UL94 standard, vertical combustion test is 1 /
The test was performed on a 16 "x 1/2" x 5 "combustion test piece.

Table 2 shows the measurement results of the obtained test pieces.

[0084]

[Table 1]

[0085]

[Table 2]

Comparative Examples 1 to 10 (A) Polymer mixture, (B) graft copolymer, (C) vinyl copolymer, (D) fluororesin, and (E) phosphate ester prepared in Reference Examples Was mixed at the compounding ratio shown in Table 1, and each physical property was measured in the same manner as in the examples.
However, in Comparative Example 9, melt kneading and extrusion were performed at a resin temperature of 250 ° C., and a test piece was formed from the obtained material at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. Table 2 shows the results of these measurements.

The following is clear from the results in Table 2.
The resin compositions of the present invention (Examples 1 to 17) are all excellent in impact resistance, heat resistance, fluidity (MFR value) and flame retardancy. Also, sufficient flame retardancy is obtained with a thickness of 2 mm or less.

On the other hand, when the blending amount of the polymer mixture (A) is 9
If it exceeds 8% by weight (Comparative Example 1), the impact resistance and the fluidity are poor, and if it is less than 10% by weight (Comparative Example 2), the flame retardancy is poor, which is not preferable.

When the amount of component (D) is less than 0.01 part by weight (Comparative Example 3), the flame retardancy is poor, and when it exceeds 5 parts by weight (Comparative Example 4), the impact resistance is poor. Not preferred.

When the amount of the phosphorus-containing compound (E) is less than 1 part by weight (Comparative Example 5), the flame retardancy is poor, and when it exceeds 40 parts by weight (Comparative Example 6), the impact resistance and heat resistance are poor. It is bad and not good.

When only the copolyester (a) or the aromatic polycarbonate (b) is used as the component (A) (Comparative Examples 7 and 8), the heat resistance deteriorates and the fluidity deteriorates, which is not preferable. .

Further, when the copolyester (a) other than the present invention is used (Comparative Example 9), the impact resistance and the fluidity deteriorate, which is not preferable.

Further, when the phosphorus-containing compound (E) other than the present invention is used (Comparative Example 10), the heat resistance deteriorates, which is not preferable.

[0094]

The thermoplastic resin composition of the present invention does not necessarily require bromine and chlorine compounds and has excellent flame retardancy, impact resistance, heat resistance, and fluidity during molding.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 69/00 C08L 69/00 // (C08L 67/02 69:00 51:04 25:12 27 : 18 83:00 61:06)

Claims (6)

[Claims] (A) (a) ethylene glycol, 1,4
-Condensed units of cyclohexanedimethanol and terephthalic acid, wherein the molar ratio of ethylene glycol units to cyclohexanedimethanol units is 95/5 to 10/90.
A polymer mixture consisting of 95 to 5% by weight of a copolyester and (b) 5 to 95% by weight of an aromatic polycarbonate, and (B) 20 to 90% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer 1 to 60% by weight and 99 to 20 parts by weight of a monomer mixture containing 0 to 79% by weight of another vinyl monomer copolymerizable therewith are mixed with a rubbery polymer 1
A graft copolymer obtained by graft copolymerization to 80 parts by weight, and / or (C) 20 to 90% by weight of an aromatic vinyl monomer and 1 to 60% by weight of a vinyl cyanide monomer, and Resin composition (a) comprising a vinyl copolymer obtained by copolymerizing a monomer mixture containing 0 to 79% by weight of another copolymerizable vinyl monomer (provided that component (A): 10-98
(D) 0.01 to 5 parts by weight of a fluorinated resin and / or 0.01 to 5 parts by weight of silicone per 100 parts by weight. (E) a thermoplastic resin composition comprising 1 to 40 parts by weight of a phosphorus-containing compound. 2. The thermoplastic resin composition according to claim 1, wherein 0.1 to 20 parts by weight of a phenol resin (F) is further added to 100 parts by weight of the resin composition (a). (E) a phosphorus-containing compound represented by the following general formula (I):
The thermoplastic resin composition according to claim 1, wherein the compound represented by the following formula is used as an essential component. Embedded image (However, the above formulas R ^{1 to} R ⁹ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Ar
^{1 to} Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. N is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ) 4. A compound represented by the formula (I):
The thermoplastic resin composition according to any one of claims 1 to 3, wherein k and m are each 1. 5. A compound represented by the formula (I):
5. The thermoplastic resin composition according to claim 3, wherein Ar ^{1 to} Ar ⁷ are the same or different and are any of phenyl, tolyl, and xylyl groups. 6. The thermoplastic resin composition according to claim 1, which is a casing molded product having a minimum thickness of 2 mm or less.